Polyoxyalkylene glycol refrigeration lubricants having pendant, non-terminal perfluoroalkyl groups

ABSTRACT

The present invention provides a composition for use in refrigeration and air-conditioning comprising: (a) at least one refrigerant selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon, and chlorofluorocarbon; and (b) a sufficient amount to provide lubrication of at least one polyoxyalkylene glycol. The polyoxyalkylene glycol has at least one pendant non-terminal perfluorinated alkyl group on its hydrocarbon polymer backbone. The polyoxyalkylene glycol is terminated with a group selected from the group consisting of hydrogen, alkyl, and fluoroalkyl. The polyoxyalkylene glycol has a molecular weight of about 300 to about 4,000 and a viscosity of about 5 to about 300 centistokes at 37° C. The polyoxyalkylene glycol is miscible in combination with the refrigerant in the range between about -40° C. and at least about +20° C.

CROSS-REFERENCE TO RELATED APPLICATION

Commonly assigned allowed U.S. Pat. No. 4,975,212 filed Dec. 27, 1988,to issue on Dec. 4, 1990, Claims a lubricating composition comprising apolyoxyalkylene glycol having a cap of a fluorinated alkyl group on atleast one end thereof wherein the polyoxyalkylene glycol is preparedfrom copolymers of ethylene and propylene oxides, ethylene and butyleneoxides, or propylene and butylene oxides.

BACKGROUND OF THE INVENTION

The present invention relates to refrigeration lubricants having apartially fluorinated polymer backbone. More particularly, the presentinvention relates to refrigeration lubricants for use withtetrafluoroethane and preferably, 1,1,1,2-tetrafluoroethane (known inthe art as R134a). R134a is a refrigerant which may replacedichlorodifluoromethane (known in the art as R12) in many applicationsbecause environmental concerns over the use of R12 exist.

R134a has been mentioned as a possible replacement for R12 becauseconcern over potential depletion of the ozone layer exists. R12 is usedin closed loop refrigeration systems; many of these systems areautomotive air-conditioning systems. R134a has properties similar tothose of R12 so that it is possible to substitute R134a for R12 withminimal changes in equipment being required. The symmetrical isomer ofR134a is R134 (1,1,2,2-tetrafluoroethane); the isomer is also similar inproperties and may also be used. Consequently, it should be understoodthat in the following discussion, "tetrafluoroethane" will refer to bothR134 and R134a.

A unique problem arises in such a substitution. Refrigeration systemswhich use R-12 generally use mineral oils to lubricate the compressor;the present discussion does not apply to absorption refrigerationequipment. See for example the discussion in Chapter 32 of the 1980ASHRAE Systems Handbook. R-12 is completely miscible with such oilsthroughout the entire range of refrigeration system temperatures whichmay range from about -45.6° to 65.6° C. Consequently, oil whichdissolves in the refrigerant travels around the refrigeration loop andgenerally returns with the refrigerant to the compressor. The oil doesnot separate during condensation, although it may accumulate because lowtemperatures exist when the refrigerant is evaporated. At the same time,the oil which lubricates the compressor contains some refrigerant whichmay affect its lubricating property.

It is known in the industry that chlorodifluoromethane (known in the artas R22) and monochlorodifluoromethane/1-chloro-1,1,2,2,2-pentafluoroethane (known in the art as R502) are not completely miscible in commonrefrigeration oils. See Downing, FLUOROCARBONS REFRIGERANT HANDBOOK, p.13. A solution to this problem has been the use of alkylated benzeneoils. Such oils are immiscible in R134a and are not useful therewith.This problem is most severe at low temperatures when a separated oillayer would have a very high viscosity. Problems of oil returning to thecompressor would be severe.

R134a is not miscible with mineral oils; consequently, differentlubricants will be required for use with R134a. However, as mentionedabove, no changes to equipment should be necessary when the refrigerantsubstitution is made. If the lubricant separates from the refrigerant,it is expected that serious operating problems could result. Forexample, the compressor could be inadequately lubricated if refrigerantreplaces the lubricant. Significant problems in other equipment alsocould result if a lubricant phase separates from the refrigerant duringcondensation, expansion, or evaporation. These problems are expected tobe most serious in automotive air-conditioning systems because thecompressors are not separately lubricated and a mixture of refrigerantand lubricant circulates throughout the entire system.

These problems have been recognized generally in the refrigeration art.Two recent publications by ASHRAE suggest that separation of lubricantsand refrigerants presents problems, although no mention is made ofR134a. These articles are Kruse et al., "Fundamentals of Lubrication inRefrigeration Systems and Heat Pumps," ASHRAE TRANSACTIONS 90(2B), 763(1984) and Spauschus, "Evaluation of Lubricants for Refrigeration andAir-Conditioning Compressors," ibid, 784.

The following discussion will be more readily understood if the mutualsolubility of refrigerants and various lubricating oils is considered ingeneral with specific reference to R134a. Small amounts of lubricantsmay be soluble in R134a over a wide range of temperatures, but as theconcentration of the lubricant increases, the temperature range overwhich complete miscibility occurs, i.e., only one liquid phase ispresent, narrows substantially. For any composition, two consolutetemperatures, i.e., a lower and a higher temperature, may exist. Thatis, a relatively low temperature below which two distinct liquid phasesare present and above which the two phases become miscible and a highertemperature at which the single phase disappears and two phases appearagain may exist. A diagram of such a system for R502 refrigerant isshown as FIG. 2 in the Kruse et al. paper mentioned above. A range oftemperatures where one phase is present exists and while it would bedesirable that a refrigeration system operate within such a range, ithas been found that for typical compositions, the miscible range oflubricants with R134a is not wide enough to encompass the typicalrefrigeration temperatures.

Disclosures which are concerned with the choice of lubricants when R134ais used as a refrigerant exist. Polyalkylene glycols were suggested tobe used in Research Disclosure 17483, October 1978 by DuPont. Specificreference was made to such oils produced by Union Carbide Corporationunder the trade names "ULCON" (sic) LB-165 and UCON 525. It is statedthat these oils are miscible in all proportions with R134a attemperatures at least as low as -50° C. It is believed that "ULCON"(sic) LB-165 and UCON 525 are polyoxypropylene glycols which have ahydroxy group at one end of each molecule and a n-butyl group at theother end.

The use of synthetic oils for refrigeration systems includingpolyoxyalkylene glycols is discussed by Sanvordenker et al. in a papergiven at an ASHRAE Symposium, June 29, 1972. The authors make the pointthat polyglycols should properly be called ethers and esters rather thanglycols because the terminal hydroxyl groups are bound by ester or ethergroups. It is stated that this substitution makes them suitable forlubrication.

U.S. Pat. No. 4,428,854 discloses the use of R134a as an absorptionrefrigerant where organic solvents are used as absorbing agents. Anexample is tetraethylene glycol dimethyl ether. A related patent U.S.Pat. No. 4,454,052 also discloses polyethylene glycol methyl ether usedas an absorbent along with certain stabilizing materials forrefrigerants such as 134a.

Japanese Patent Publication 96684 dated May 30, 1985 addresses thestability problems of refrigerants. The reference teaches that perfluoroether oligomers are one class of useful lubrication oils.

U.S. Pat. No. 4,267,064 also recommends the use of polyglycol oils,particularly for rotary compressors. It is indicated that viscosities inthe range of 25-50 centistokes (CS) at 98.9° C. are needed plus aviscosity index greater than 150. Many refrigerants are mentioned butnot tetrafluoroethane.

Japanese published application No. 51795 of 1982 relates to antioxidantsand corrosion inhibitors for use with various polyether type syntheticoils. The tests were carried out with R-12, which does not exhibit theimmiscible character of R134a.

Japanese published patent application 96,684 published May 30, 1985addresses the stability problems of refrigerants. The reference mentions12 refrigerants including tetrafluoroethane. The reference also teachessix classes of lubricants including perfluoro ether oligomer,fluorinated silicone, fluorinated oxethane, chlorotrifluoro ethylenepolymer, fluorinated polyphenyl ether, and perfluoroamine.

U.S. Pat. No. 4,431,557 relates to additives used in synthetic oils.Many refrigerants are mentioned, but not tetrafluoroethane, and thepatentees gave no indication of concern for miscibility of therefrigerants and the lubricants.

Commonly assigned U.S. Pat. No. 4,755,316 teaches a compressionrefrigeration composition. The refrigerant is tetrafluoroethane whilethe lubricant is at least one polyoxyalkylene glycol which is at leastdifunctional with respect to hydroxyl groups, has a molecular weightbetween 300 and 2,000, has a viscosity of about 25-150 centistokes at37° C., has a viscosity index of at least 20, and is miscible incombination with the tetrafluoroethane in the range between -40° C. andat least +20° C. The reference does not teach or suggest the presentrefrigeration compositions. See also U.S. Pat. No. 4,948,525.

U.K. Patent 1,087,283; U.S. Pat. Nos. 3,483,129; 4,052,277; 4,118,398;4,379,768; 4,443,349; 4,675,452; 4,827,042; 4,898,991; and 4,931,199;International Publications WO 87/02992 and WO 87/02993; and Kokai PatentPublication 118,598 published May 11, 1989 teach perfluorinated ethersand perfluoropolyethers as lubricants. The references do not teach thattheir lubricants are useful with R134a. Also, Kokai Patent Publication146,996, published June 30, 1987, teaches the addition of aperfluoroalkylpolyether as an extreme pressure additive to mineral oil.

Carre, "The Performance of Perfluoropolyalkyether Oils under BoundaryLubrication Conditions", TRIBOLOGY TRANSACTIONS 31(4), 437 (1987) andCarre, 1988 Air Force Report discuss the problems ofperfluoropolyalkylethers and boundary lubrication in spacecraft.

U.K. Patent 1,354,138 teaches compounds of the formula:

    R--(--[(L)(CH).sub.z --CH.sub.2 --O--].sub.x --R.sub.f).sub.m

wherein L is --H or --CH₃ and z is 0, 1, or 2 on page 1, lines 9-41. Assuch, the oxyalkylene group can be oxymethylene when z is 0, ethyleneoxide when z is 1 and L is --H, straight chain propylene oxide when z is2 and L is --H, branched propylene oxide when z is 1 and L is --CH₃, andbranched oxypentylene when z is 2 and L is --CH₃. These materials aretaught to be useful as surfactants.

U.S. Pat. No. 4,079,084 teaches a compound having a chain of repeatingunits which may be oxyalkylidine, oxymethylene, oxyalkylene, iminoalkylene, or secondary amido chains and at least two terminalperfluorocarbon groups of at least three carbon atoms. For theoxyalkylene unit, the reference teaches ethylene oxide, propylene oxide,or butylene oxide. These materials are taught to be useful assurfactants.

U.S. Pat. No. 2,723,999 teaches compounds of polyethylene glycols orpolypropylene glycols. These materials are taught to be useful assurface active agents.

U.S. Pat. No. 4,359,394 teaches that a minor portion of an additive suchas a fluorinated aromatic, for example, benzotrifluoride, can be addedto a conventional lubricant such as mineral oil. The reference does notteach that a fluorinated aromatic alone is useful as a lubricant.

U.S. Pat. No. 4,944,890 teaches a refrigerant composition of R134a and acopolymer of a fluorinated olefin and nC₄ H₉ OCH═CH₂.

Because it is expected that R134a will become widely used in the fieldof refrigeration and air-conditioning, new improved lubricants usefulwith R134a are needed in the art.

SUMMARY OF THE INVENTION

Considering that perfluorinated ethers and perfluoropolyethers areimmiscible with R134a over a wide temperature range so as to beunsuitable as lubricants for automotive air-conditioning purposes, it issurprising that polyoxyalkylene glycol compositions having at least onependant non-terminal perfluorinated alkyl group on their hydrocarbonpolymer backbone are miscible with a refrigerant selected from the groupconsisting of hydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon,and chloroflorocarbon. More particularly, the present lubricants aremiscible with tetrafluoroethane. It is even more surprising thatpolyoxyalkylene glycol compositions having pendant non-terminal alkylgroups on their hydrocarbon polymer backbone wherein at least about 40%of the non-terminal pendant alkyl groups are perfluorinated haveimproved miscibility when compared with the polyoxyalkylene glycolshaving a cap of a fluorinated alkyl group on at least one end thereof ofallowed commonly assigned U.S. Pat. NO. 4,975,212.

As such, the present invention provides a composition for use incompression refrigeration and air-conditioning comprising: (a) arefrigerant selected from the group consisting of hydrofluorocarbon,hydrochlorofluorocarbon, fluorocarbon, and chlorofluorocarbon; and (b) asufficient amount to provide lubrication of at least one polyoxyalkyleneglycol.

The polyoxyalkylene glycol has pendant non-terminal alkyl groups on itshydrocarbon polymer backbone wherein of the total number of pendantnon-terminal alkyl groups in the polyoxyalkylene glycol, at least one ofthe pendant alkyl groups is perfluorinated or in other words, at leastabout 2% of the pendant alkyl groups are perfluorinated. Thepolyoxyalkylene glycol is terminated with a group selected from thegroup consisting of hydrogen, alkyl, and fluoroalkyl. Thepolyoxyalkylene glycol has a molecular weight between about 300 andabout 4,000, and a viscosity of about 5 to about 300 centistokes at 37°C. The polyoxyalkylene glycol is miscible in combination withtetrafluoroethane in the range between -40° C. and at least +20° C.Preferably, the viscosity of the polyoxyalkylene glycol is about 5 toabout 150 centistokes at 37° C.

Preferably, the present lubricants have at least about 40% of theirpendant non-terminal alkyl groups as perfluorinated groups. When used incombination with R134a, these lubricating compositions provide improvedranges of miscibility. Comparable to the fluorinated refrigerationlubricants of commonly assigned allowed U.S. Pat. No. 4,975,212, thepresent lubricants when used with R134a have low upper critical solutiontemperatures (UCST) which are consistent over a range of viscositiestaken at 37° C. Although the compositions of commonly assigned allowedU.S. Pat. No. 4,975,212 exhibit wide miscibility ranges, it has beenfound that the present lubricants have higher lower critical solutiontemperatures (LCST), over a range of viscosities taken at 37° C.,compared with the lubricants of commonly assigned allowed U.S. Pat. No.4,975,212. The term "higher lower critical solution temperatures" asused herein means the following For the known lubricants of commonlyassigned allowed U.S. Pat. No. 4,975,212, assume that with a first fixedviscosity at 37° C., the miscibility range with R134a extends to a LCSTof T1. In contrast with the present lubricants at the same viscosity,the miscibility range with R134a extends to a LCST of T2 wherein T2>T1.This unexpectedly superior property provides better operations at highertemperatures due to improved miscibility. Thus, the present lubricantswhen used with R134a are advantageous to use because they have widemiscibility ranges with consistent low UCSTs and higher LCSTs.

The present invention also provides a method for improving lubricationin refrigeration and air-conditioning equipment using a refrigerantselected from the group consisting of hydrofluorocarbon,hydrochlorofluorocarbon, fluorocarbon, and chlorofluorocarbon. Themethod comprises the step of: employing as a lubricant at least onepolyoxyalkylene glycol. The polyoxyalkylene glycol has at least onependant non-terminal perfluorinated alkyl group on its hydrocarbonpolymer backbone. The polyoxyalkylene qlycol is terminated with a groupselected from the group consisting of hydrogen, alkyl, and fluoroalkyl.The polyoxyalkylene qlycol has a molecular weight of about 300 to about4,000 and a viscosity of about 5 to about 300 centistokes at 37° C. Thepolyoxyalkylene glycol is miscible in combination with thetetrafluoroethane in the range between about -40° C. and at least about+20° C.

Other advantages of the present invention will become apparent from thefollowing description and appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Refrigerants

The present lubricating compositions may be used in most lubricatingapplications but they are particularly useful with R134a.

The invention relates to the substitution of tetrafluoroethane, andpreferably, 1,1,1,2-tetrafluoroethane for R-12 which has been consideredto present a danger to the atmospheric ozone layer. R134a has physicalcharacteristics which allow its substitution for R-12 with only aminimum of equipment changes although it is more expensive andunavailable in large quantities at the present time. Its symmetricalisomer, R134, may also be used. The detrimental effect oftetrafluoroethane on atmospheric ozone is considered to be much lessthan the effect of R-12, and therefore, the substitution oftetrafluoroethane for R-12 is considered probable in the future.

Until R134a becomes available in commercial quantities, it may beproduced by any known method including reacting ethylene with carbonhaving elemental fluorine adsorbed therein as taught by commonlyassigned U.S. Pat. No. 4,937,398 which is incorporated herein byreference.

It has been found that the present lubricants are also suitable for usewith R12, R22, and R502 which are all refrigerants now available incommercial quantities. A composition for use in refrigeration andair-conditioning comprising: (a) R12, R22, or R502; and (b) the presentnovel lubricating compositions may be used until 134a becomes availablein commercial quantities. When R134a is available in commercialquantities, it may be useful to blend R134a with R12, R22, or R502.R134a, R12, R22, or R502 may also be blended with one of the following:methylene fluoride (known in the art as R32),1-chloro-1,1,2,2-tetrafluoroethane(known in the art as R124a),pentafluoroethane (known in the art as R125),1-chloro-1,1-difluoroethane(known in the art as R142b),1,1,1-trifluoroethane (known in the art as R143a),1,1-difluoroethane(known in the art as R152a), andcycloperfluorobutane(known in the art as RC318). However, it should beunderstood that only refrigerant blends and more specifically, blends oftetrafluoroethane with other refrigerants which are miscible with thelubricants of the invention in the range of about -40° C. to at least+20° c., are included.

R-12 is used in very large quantities and of the total, a substantialfraction is used for automotive air-conditioning. Consequently, theinvestigation of the lubricants needed for use with R134a (or R134) hasemphasized the requirements of automotive air-conditioning since thetemperature range is generally higher than that of other refrigerationsystems, i.e., about 0° C. to 93° C. Since it has been found that R134adiffers in being much less miscible with common lubricants than R-12,the substitution of refrigerants becomes more difficult.

Lubricants

R-12 is fully miscible in ordinary mineral oils and consequently,separation of the lubricants is not a problem. Although it is similar toR12, R134a is relatively immiscible in many lubricants as may be seen byreference to commonly assigned U.S. Pat. No. 4,755,316. Thus, it isnecessary to find suitable lubricants which are miscible with R134a (orR134) to avoid refrigerant and lubricant separation.

It is characteristic of some refrigerant-lubricant mixtures that atemperature exists above which the lubricant separates. Since thisphenomenon occurs also at some low temperatures, a limited range oftemperatures within which the two fluids are miscible may occur.Ideally, this range should span the operating temperature range in whichthe refrigerant is to operate, but often this is not possible. It istypical of automotive air-conditioning systems that a significantfraction of the circulating charge is lubricant and the refrigerant andlubricant circulate together through the system. Separation of thelubricant and refrigerant as they return to the compressor could resultin erratic lubrication of the moving parts and premature failure. Otherair-conditioning system types usually circulate only the relativelysmaller amount of lubricant which is carried by the refrigerant gaspassing through the compressor and should be less sensitive to theseparation problem. Especially with automotive air-conditioning,separation of the relatively large amount of lubricant circulating withthe refrigerant can also affect the performance of other parts of thesystem.

In a typical automotive air-conditioning system, the temperatures atwhich the refrigerant is condensed originally will be about 50°-70° C.but may reach 90° C. in high ambient temperature operation. Thecondensation of hot refrigerant gases in the condensing heat exchangercan be affected if the exchanger is coated with lubricant preferentiallyso that condensation of the refrigerant occurs by contact with thelubricant film. Thereafter, the two-phase mixture of lubricant andrefrigerant must pass through a pressure reduction to the lowtemperature stage where the refrigerant evaporates and absorbs the heatgiven up in cooling air and condensing moisture. If lubricant separatesat the condenser, then the performance of the evaporator stage can beaffected if separate phases persist as the two-phase mixture passesthrough the pressure reduction step. As with the condenser, accumulationof lubricant on the evaporator coils can affect heat exchangeefficiency. In addition, the low evaporator temperatures may result inexcessive cooling of the lubricant resulting in a more viscous liquidand trapping of the lubricant in the evaporator. These problems can beavoided if the lubricant and the refrigerant are fully misciblethroughout the operating temperature ranges, as was true with R-12 andmineral oil mixtures. R134a, with its limited ability to dissolvelubricants, presents a problem which must be solved.

Preferably, the lubricating composition comprises the Formula (I):

    R'[(R.sub.f)CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n R'

wherein R' is selected from the group consisting of hydrogen, alkyl, orfluoroalkyl; m is 2 to 40; n is 0 to 60; R is selected from the groupconsisting of hydrogen and alkyl, and R_(f) is a perfluoroalkyl group.Preferred R' alkyl groups have 1 to 12 carbon atoms and can be straightchain or branched. Examples include methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and thelike.

Preferred fluoroalkyl groups are of the Formula (II):

    --(CH.sub.2).sub.x (CF.sub.2).sub.y CH.sub.3

wherein x is 1 to 4 and y is 0 to 15. More preferably, x is 1 and y is 0so that at least one of R is a fluorinated alkyl group of the formula--CH₂ CF₃ or x is 1 and y is 2 so that at least one of R is afluorinated alkyl group of the formula --CH₂ (CF₂)₂ CH₃. The fluorinatedalkyl group may also be branched.

preferred R alkyl groups have 1 to 5 carbon atoms and include methyl,ethyl, n-propyl, isopropyl, n-butyl, Sec-butyl, tert-butyl, n-pentyl,isopentyl, neopentyl, and the like.

Preferred perfluoroalkyl groups are of the Formula (III):

    C.sub.n F.sub.2n+1

wherein n is 1 to 8 and include perfluoromethyl, perfluoroethyl,perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl,perfluoroheptyl, and perfluorooctyl.

As such, the present lubricating composition may be terminated by ahydrogen at one end and an alkyl group at the other end, by a hydrogenat one end and a fluorinated alkyl group at the other end, by an alkylgroup at one end and a fluorinated alkyl group at the other end, by ahydrogen at both ends, by an alkyl group at both ends, or by afluorinated alkyl group at both ends.

Preferably, at least 40% of the non-terminal pendant alkyl groups areperfluorinated. As such, the ratio of m to n is Formula (I) above is atleast 2:3.

Preferred lubricating compositions are

    HO[R.sub.f CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n H

    CH.sub.3 O[R.sub.f CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.3

    CF.sub.3 CH.sub.2 O[R.sub.f CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.2 CF.sub.3

    C.sub.3 F.sub.7 CH.sub.2 O[R.sub.f CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.2 C.sub.3 F.sub.7

where m is 2 to 40 and n is 0 to 60.

The most preferred lubricating compositions are:

    HO--[R.sub.f CHCH.sub.2 O].sub.m H

    CH.sub.3 O[R.sub.f CHCH.sub.2 O].sub.m CH.sub.3

    CF.sub.3 CH.sub.2 O[R.sub.f CHCH.sub.2 O].sub.m CH.sub.2 CF.sub.3

    C.sub.3 F.sub.7 CH.sub.2 O[R.sub.f CHCH.sub.2 O].sub.m OCH.sub.2 C.sub.3 F.sub.7

where m is 2 to 40.

The lubricating compositions may be formed by any known method includingpolymerizing 3,3,3-trifluoro-1,2-epoxypropane as taught by F. Trischleret al.,"Preparation of Fluorine-Containing Polyethers", J. of PolymerScience 5(A-1),2313 (1967).

Commercially available 3,3,3-trifluoro-1,2-epoxypropane may be used or3,3,3-trifluoro-1,2-epoxypropane may be prepared by any known methodincluding dehydrohalogenation of 3-bromo-1,1,1-trifluoro-2-propanol astaught by E. McBee et al., "The Preparation and Properties of3,3,3-Trifluoro-1,2-Epoxypropane", J. Amer. Chem. Soc. 74, 3022 (1952).The 3-bromo-1,1,1-trifluoro-2-propanol may be prepared by thebromination of commercially available trifluoroacetone to form3-bromo-1,1,1-trifluoropropanone which may then be reduced with lithiumaluminum hydride.

Preferably, the lubricating compositions are prepared by reacting3,3,3-trifluoro-1,2-epoxypropane with either an anionic or cationicinitiator at elevated temperature. The lubricating compositions areisolated directly from the reaction mixture.

The present lubricants have higher low critical solution temperatureswhen used with R134a and consequently, they are an improvement on thecompositions of tetrafluoroethane and fluorinated polyoxyalkyleneglycols of commonly assigned allowed U.S. Pat. No. 4,975,212. Thepresent lubricants operate without separation from R134a over much ofthe operating temperature range. Any separation which does occur wouldpreferably be at the higher temperatures, and thus, would affect thecondenser rather than the lower temperature evaporator.

A blend of the present lubricating compositions wherein the compositionshave different molecular weights may be used in practicing the presentinvention.

The present lubricating compositions are miscible in combination withtetrafluoroethane in the range between about -40° C. and at least about+20° C., preferably at least about +30° C., more preferably at leastabout +40° C., and most preferably at least about +50° C.

Preferably, the tetrafluoroethane and lubricant are used in a weightratio of about 99:1 to about 1:99, and more preferably, in a weightratio of about 99:1 to about 70:30.

The range of miscibility is not the only factor to be considered whenone is selecting a lubricant for automotive air-conditioning service (orother refrigeration applications). Lubricating properties also must besatisfactory for the intended application. Practically, this means thatfor automotive air conditioning, the viscosity of the lubricant will beabout 5-150 centistokes, preferably about 100 centistokes (CS) at 37° C.with a viscosity index of at least 20 in order that the lubricant issufficiently viscous at high temperatures to lubricate while remainingsufficiently fluid to circulate around the refrigeration circuit at lowtemperatures. The range of viscosity may also be expressed as about 3-24CS at 98.9° C. In addition, the lubricant should be chemically stableand not cause corrosion or other problems in long-term service. Otherfactors which should be considered in selecting lubricants arecompatibility, lubricity, safety, and the like.

Additives which may be used to enhance performance include (1) extremepressure and antiwear additives, (2) oxidation and thermal stabilityimprovers, (3) Corrosion inhibitors, (4) viscosity index improvers, (5)pour and floc point depressants, (6) detergent, (7) anti foaming agents,and (8) viscosity adjusters.

Typical members of these classes are listed in TABLE 1 below.

                  TABLE 1                                                         ______________________________________                                        Class Additive                                                                            Typical Members of the Class                                      ______________________________________                                        1.  Extreme     phosphates, phosphate esters (bicresyl                            pressure    phosphate), phosphites, thiophosphates                            and anti-   (zinc diorganodithiophosphates) chlori-                           wear        nated waxes, sulfurized fats and                                              olefins, organic lead compounds, fatty                                        acids, molybdenum complexes, halogen                                          substituted organosilicon compounds,                                          borates, organic esters, halogen substi-                                      tuted phosphorous compounds, sulfurized                                       Diels Alder adducts, organic sulfides,                                        compounds containing chlorine and                                             sulfur, metal salts of organic acids.                         2.  Oxidation and                                                                             sterically hindered phenols (BHT), aro-                           thermal     matic amines, dithiophosphates,                                   stability   phosphites, sulfides, metal salts of                              improvers   dithio acids.                                                 3.  Corrosion   organic acids, organic amines, organic                            Inhibitors  phosphates, organic alcohols, metal                                           sulfonates, organic phosphites.                               4.  Viscosity   polyisobutylene, polymethacrylate, poly-                          index       alkylstyrenes.                                                    improvers                                                                 5.  Pour Point &/                                                                             polymethacrylate ethylene-vinyl                                   or floc point                                                                             acetate copolymers, succinamic acid-                              depressants olefin copolymers, ethylene-alpha                                             olefin copolymers, Friedel-Crafts                                             condensation products of wax with                                             naphthalene or phenols.                                       6.  Detergents  sulfonates, long-chain alkyl substi-                                          tuted aromatic sulfonic acids,                                                phosphonates, thiophosphonates,                                               phenolates, metal salts of alkyl                                              phenols, alkyl sulfides, alkylphenol-                                         aldehyde condensation products, metal                                         salts of substituted salicylates,                                             N-substituted oligomers or polymers                                           from                                                                          the reaction products of unsaturated                                          anhydrides and amines,                                                        copolymers of methacrylates with                                              N-substituted compounds such as                                               N-vinyl pyrrolidone or                                                        dimethylaminoethyl methacrylate,                                              copolymers which incorporate poly-                                            ester linkages such as vinyl acetate-                                         maleic anhydride copolymers.                                  7.  Anti-Foaming                                                                              silicone polymers                                                 Agents                                                                    8.  Viscosity   Polyisobutylene, polymethacrylates,                               Adjusters   polyalkylstyrenes, naphthenic oils,                                           alkylbenzene oils, paraffinic oils,                                           polyesters, polyvinylchloride,                                                polyphosphates.                                               ______________________________________                                    

The present invention is more fully illustrated by the followingnon-limiting Examples.

COMPARATIVES 1-5

Comparatives 1-5 demonstrate that perfluorinated ethers andperfluoropolyethers are not useful as lubricants with R134a because theyare immiscible with R134a over a wide temperature range which isunsuitable for automotive air-conditioning purposes. Most automotiveair-conditions operate at about 0° to 93° C. and useful lubricantsoperated at about -30° to 93° C. Table 2 contains the results of theComparatives. The viscosities are at 37° C.

                                      TABLE 2                                     __________________________________________________________________________                     VISC.   ETHER MISC                                           COMP. ETHER      (CS) MW WT. % (°C.)                                   __________________________________________________________________________    1     KRYTOX 143AB                                                                             85   3700                                                                             15    Immiscible                                           (Dupont)                 at and                                               (registered trademark)   below 10.2                                     2     KRYTOX 143AX                                                                             150  4800                                                                             15    Immiscible                                           (registered trademark)   at and                                                                        below 20.4                                     3     KRYTOX 143CZ                                                                             125  4400                                                                             15    Immiscible                                           (registered trademark)   at and                                                                        below 19.6                                     4     BRAYCO 1724                                                                              65.5 -- 15    Immiscible                                           (Bray)                   at and                                               (registered trademark)   below 18.4                                     5     S-100      100  4600                                                                             15    Immiscible                                           (Daikin)                 at and                                               (registered trademark)   below 30.0                                     __________________________________________________________________________

COMPARATIVES 6-10

For comparative purposes, the following Table 3 was generated based onthe compositions of R134a and fluorinated polyoxyalkylene glycols ofallowed commonly assigned U.S. Pat. No. 4,875,212. The fluorinatedpolyoxyalkylene glycols have the formula

    CF.sub.3 CH.sub.2 OCH(CH.sub.3)CH.sub.2 O[CH.sub.2 CH(CH.sub.3)O].sub.m CH.sub.2 CF.sub.3

                  TABLE 3                                                         ______________________________________                                                              VISC.  EX     MISC                                      COMP.  m      MW      (CS)   WT. %  (°C.)                              ______________________________________                                        6      15      991    33     14     -60 to over 70                            7      20     1366    56     14     -60 to over 80                                                         50     -60 to over 70                            8      26     1666    78     14     -60 to 67                                                              50     -60 to over 70                            9      29     1866    91      6     -60 to 64.2                                                            15     -60 to 59.5                                                            22     -60 to 63.3                                                            30     -60 to 67                                                              39     -60 to 75                                                              50     -60 to 74                                 10     34     2166    127    14     -60 to 42.6                                                            50     -60 to over 70                            ______________________________________                                    

EXAMPLES 1-9

Examples 1 to 9 are directed to the preparation of lubricants useful inthe present invention.

EXAMPLE 1

This Example is directed to the preparation ofpoly(trifluoromethylethyleneglycol) which has the formulaHO--[(CF₃)CHCH₂ O]_(m) H wherein m is about 10.

3,3,3-Trifluoro-1,2-epoxypropane (300grams, 2.68 moles) andborontrifluoride-etherate were reacted in a 600 milliliter autoclave atan initial temperature of -78° C. During the course of the reaction (2hours), the temperature was allowed to warm to ambient conditions (27°C.). After this period, residual pressure was vented from the system.Ether (200 milliliters) was added to dissolve the product. The ethersolution was washed with saturated sodium bicarbonate, dried (MgSO₄),and distilled from the product. Yield of the polymer which was isolatedas a light yellow oil was 210 grams (70%). Analysis of the product gavean hydroxyl number value of 102 which corresponds to a molecular weightof 1100.

EXAMPLE 2

This Example is also directed to the preparation ofpoly(trifluoromethylethyleneglycol) which has the formulaHO--[(CF₃)CHCH₂ O]_(m) H wherein m is 24.

The product of this reaction was identical to that of Example 1, exceptthat the molecular weight was increased to give a more viscous product.This transformation was accomplished by using aluminum chloride as theFriedel-Crafts catalyst. Yield of the polymer which was isolated as aclear, colorless oil was 221 grams (74%). Analysis of the product gavean hydroxyl number of 40 which corresponds to a molecular weight of2800.

EXAMPLE 3

This Example is also directed to the preparation ofpoly(trifluoromethylethyleneglycol) which has the formulaHO--[(CF₃)CHCH₂ O]_(m) H wherein m is 36.

The product of this reaction was identical to Example 1, except that thecatalyst was changed to increase the molecular weight. For this Example,potassium hydroxide was used as the anionic initiator. Yield of polymerisolated as a colorless oil was 174 grams (58%). Analysis of the productgave an hydroxyl number of 28 which corresponds to a molecular weight of4000.

EXAMPLE 4

This Example is directed to the preparation ofalpha,omega-dimethyl(polytrifluoromethylethyleneglycol) which has theformula CH₃ O--[(CF₃)CHCH₂ O]_(m) CH₃ wherein m is 10.

The polymeric diol isolated in Example 1 (100 grams, 0.1 mole) wasdissolved in butylether (100 milliliters). Triethylamine (26.3 grams,0.26 mole) was added and the reaction mixture cooled to 5° C.Methanesulfonylchloride (25.2 grams, 0.22 mole) was added dropwise.After stirring for 4 hours, the reaction was quenched with hydrochloricacid (6N, 100 milliliters). The resulting phases were separated and theether layer was washed with an additional hydrochloric acid wash (6N,100 milliliters). Finally, the ether layer was washed with ammoniumhydroxide (7N, 100 milliliters), dried and the solvent was removed toyield the dimesylate of poly(trifluoromethylethyleneglycol). Yield 113grams (90%).

The dimesylate was reacted with sodium methoxide (11.9grams, 0.22 mole)in butylether (200 milliliters) at 85° C. for 6 hours. Workup asdescribed above yielded the dimethyl product as a colorless oil. Yield92 grams (90%).

EXAMPLE 5

This Example is directed to the preparation ofalpha,omega-bis-1,1,1-trifluoroethylpoly(trifluoromethylethylene glycol)which has the formula CF₃ CH₂ O[(CF₃)CHCH₂ O]_(m) CH₂ CF₃ wherein m is10.

This material was prepared similar to that described in Example 4 exceptthat the alkoxide was changed to sodium trifluoroethanolate. Yield ofthe colorless oil was 102 grams (90%).

EXAMPLE 6

This Example is directed to the preparation ofalpha,omega-bis-1H,1H-heptafluorobutylpoly(trifluoromethylethyleneglycol)which has the formula CF₃ (CF₂)₂ CH₂ O--[(CF₃)CHCH₂ O]CH₂ (CF₂)₂ CF₃wherein m is 10.

This material was prepared in a manner to that described in Example 4,except that the alkoxide was changed to 1H,1H-heptafluorobutanoate.Yield of the colorless oil was 118.5grams (90%).

EXAMPLE 7

This Example is directed to the preparation ofalpha,omega-bis-trifluoroethyl-poly[(trifluoromethylethylene)(propylene)]glycol which has the formula CF₃ CH₂ O[(CF₃)CHCH₂ O]_(m)[(CH₃)CHCH₂ O]_(n) CH₂ CF₃ where m is 2 and n is 25 which equals 7%non-terminal pendant perfluorinated alkyl groups and a molecular weightof 1,852.

36.3 grams (0.62 mole) of propylene oxide, 10 grams (0.089 mole) oftrifluoropropylene oxide, and 0.02 milliliter of boron trifluorideetherate were reacted in a 300 milliliter autoclave at ambienttemperature for 2 hours at 29° C. Residual pressure was vented. 200milliliters of ether were added to dissolve the product. The productsolution was washed with saturated NaHCO₃ (2×50 milliliters) and thendried over MgSO₄. The ether was removed by distillation to leave ayellow oil. The yield was 33.3 grams (72%). Analysis of the product gavea hydroxyl number of 66 which corresponds to a molecular weight of1,690.

The preceding product was reacted with 4.5 grams (0.039 mole) MsCl, 5grams (0.049 mole) Et₃ N, and 150 milliliters of Bu₂ O to form thedimesylate. The MsCl was slowly added to the product solution in Bu₂O/Et₂ N at 0° C. After addition of MsCl was complete after about tenminutes, the reaction was warmed to room temperature to complete theformation of dimesylate. The precipitated salt was removed byfiltration, the filter cake was washed with 50 milliliters of Bu₂ O, andthe filtrates were combined. By NMR and IR analysis, the capping wasquantitative.

The preceding product was then added to a solution containing 0.041 moleof NaOCH₂ CF₂ in 50 milliliters of Bu₂ O. The reaction temperature wasraised to 110° C. for two hours. The reaction was cooled in an ice bathto 0° C. and the NaOMs salt filtered. The filter cake was washed with 50milliliters Bu₂ O and the filtrates were combined. The product waswashed with 2×50 milliliters 3N HCl and then 1×50 milliliters 5% NH₄ OH.The organic layer was dried over MgSO₄, filtered and the solvent removedunder reduced pressure. A viscous oil of 92 centistokes at 37° C. wasobtained. The yield of yellow oil was 30.7 grams (85%).

EXAMPLE 8

This Example is directed to the preparation ofalpha,omega-bis-trifluoroethyl-poly[(trifluoromethylethylene)(propylene)]glycol which has the formula CF₃ CH₂ O[(CF₃)CHCH₂ O]_(m)(CH₃)CHCH₂ O]_(n) CH₂ CF₃ where m is 9 and n is 13 which equals 41%non-terminal pendant perfluorinated alkyl groups and a molecular weightof 1,940.

25 grams (0.22 mole) of trifluoropropene oxide and 18.7 grams (0.32mole) of propylene oxide were charged into a 300 milliliter autoclave.The autoclave was cooled to -78° C. and 0.2 milliliter of borontrifluoride etherate was added. The autoclave was warmed to 28° C. andmaintained at this temperature for two hours. Excess pressure was ventedand the product dissolved in 200 milliliters of Et₂ O. The organic phasewas washed with 2×50 milliliters of saturated NaHCO₃, dried over MgSO₄,and then the solvent was removed under reduced pressure. A clearcolorless oil resulted. The yield was 33.6 grams (77%). Analysis of theproduct gave a hydroxyl number of 64 which corresponds to a molecularweight of 1750.

The resulting diol was converted to the dimesylate by reacting 33 gramsof the product in 200 milliliters of Bu₂ O containing 50 milliliters ofEt₃ N with 4.7 grams of MsCl at 0° C. After the addition was complete,the reaction was warmed to room temperature and stirred for one hour.The salts were removed by filtration, the filter cake was washed with 50milliliters of Bu₂ O, and the filtrates were combined. Based on NMR andIR, the conversion was quantitative.

The resulting dimesylate was reacted with a solution of Bu₂ O (50milliliters) containing 0.4 mole of NaOCH₂ CF₃. The reaction wasmaintained at 110° C. for two hours. The reaction was then cooled to 0°C. and the precipitate NaOMs removed by filtration. The filter cake waswashed with 25 milliliters of Bu₂ O and the filtrates were combined. TheBu₂ O/product solution was washed with 2×100 milliliters of 3N HCl andthen 50 milliliters of 5% NH₄ OH. The organic phase was then dried overMgSO₄. The Bu₂ O was removed by vacuum distillation. A clear yellow oilwith a viscosity of 93 centistokes at 37° C. was isolated.

EXAMPLE 9

This Example is directed to the preparation of alpha,omega-bis-trifluoroethyl-poly[(trifluoroethylene)(ethyl ene)]glycolwhich has the formula

    CF.sub.3 CH.sub.2 O[(CF.sub.3)CHCH.sub.2 O].sub.m [CH.sub.2 CH.sub.2 O].sub.n CH.sub.2 CG.sub.3

where m is 12 and n is 18 which equals 40% non-terminal pendantperfluorinated alkyl groups and a molecular weight of 2,315±30.

50 grams (0.446 mole) trifluoropropene oxide and 29 grams (0.669 mole)ethylene oxide were added to a 300 milliliter autoclave. The autoclavewas cooled to -8° C. and 0.2 milliliter of boron trifluoride etheratewas added. The contents were warmed to 30° C. and maintained for twohours. Excess pressure was vented. The contents were dissolved in 200milliliters of Bu₂ O and then washed with 2×50 milliliters of saturatedNaHCO₃. After drying over MgSO₄, the ether was removed to yield a yellowviscous oil contaminated with a white solid residue. The precipitate wasremoved by filtration and appeared to be polyethylene. The remainingliquid was the mixed diol. A hydroxyl number of 52 was obtained whichcorresponded to a molecular weight of 2,150±30. The yield was 45.8 grams(58%).

40 grams of the diol, 200 milliliters Bu₂ O, and 5 grams of Et₃ N weremixed and cooled to 0° C. 4.7 grams of MsCl were added dropwise over aten minute period. Stirring was maintained for two hours. Theprecipitated solids were removed by filtration and the filter cake waswashed with 50 milliliters Bu₂ O. The filtrates were combined. NMR andIR analysis indicated that the reaction is quantitative.

The preceding solution was added to a Bu₂ O solution containing 0.041mole of NaOCH₂ CF₃. The reaction was heated to 110° C. for two hours andthen cooled to 0° C. The precipitated salts of NaOMs were removed byfiltration and the filter cake was washed with 50 milliliters of Bu₂ O.The combined filtrates were washed with 2×100 milliliters of 3N HCl andthen 100 milliliters of 5% NH₄ OH. The organic phase was dried overMgSO₄. Bu₂ O was removed by vacuum distillation. The thick viscous oilwas isolated. The yellow oil had a viscosity of 135 centistokes at 37°C.

The miscibility of the lubricating compositions was determined bycombining them with refrigerant in a glass tube and observing theresults when the tubes were maintained at preselected temperatures. Atube was filled with the desired amount of lubricant and thenrefrigerant was added while the oil was frozen in liquid nitrogen. Thetube was then sealed and immersed in a thermostated bath. After thetemperature was equilibrated, the miscibility of the lubricant andrefrigerant was determined by visual observation. The results of thetests made with R-134a and the lubricating compositions of Examples 1-9are shown in Table 4 below. Because the critical temperature of R134a is93° C., the miscibility apparatus was cut off at 80° C. for safetyreasons.

                  TABLE 4                                                         ______________________________________                                        VISC. (CS)   MW      EX WT %    MISC (°C.)                             ______________________________________                                        Ex. 1                                                                              84          1100    14       -60 to over 80                              Ex. 2                                                                              190         2750    14       -60 to over 80                              Ex. 3                                                                              >300        4000    14       -60 to over 80                              Ex. 4                                                                              40          1128    14       -60 to over 80                              Ex. 5                                                                              52          1264    14       -60 to over 80                              Ex. 6                                                                              73          1464    14       -60 to over 80                              Ex. 7                                                                              92          1852    15       -60 to 61.3                                 Ex. 8                                                                              93          1940    15       -60 to 76                                   Ex. 9                                                                              135         2315    14       -60 to 67                                   ______________________________________                                    

EXAMPLES 10-225

The following lubricants are combined with each of R12 and R134a and themiscibility is determined as described for Examples 1-9 above; eachlubricant exhibits satisfactory miscibility. MW stands for molecularweight.

    ______________________________________                                        EX    Lubricant                   MW                                          ______________________________________                                         10   HO--[(F.sub.3 C)CH--CH.sub.2 --O].sub.3 --CH.sub.3                                                          368                                        11   HO--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.8 --CH.sub.3                                                  1,328                                        12   HO--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.12 --CH.sub.3                                                 2,576                                        13   HO--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.15 --CH.sub.3                                                 3,958                                        14   HO--[(F.sub.3 C)CH--CH.sub.2 --O].sub.3 --C.sub.2 H.sub.5                                                   382                                        15   HO--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.9 --C.sub.2 H.sub.5                                           1,504                                        16   HO--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.13 --C.sub.2 H.sub.5                                          2,802                                        17   HO--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.15 --C.sub.2 H.sub.5                                          3,976                                        18   HO--[(F.sub.3 C)CH--CH.sub.2 --O].sub.6 --C.sub.3 H.sub.7                                                   732                                        19   HO--[(F.sub.5 C.sub.2)CH--CH.sub. 2 --O].sub.10 --C.sub.3 H.sub.7                                         1,680                                        20   HO--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.14 --C.sub.3 H.sub.7                                          3,028                                        21   HO--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.12 --C.sub.3 H.sub.7                                          3,204                                        22   HO--[(F.sub.3 C)CH--CH.sub.2 --O].sub.7 --C.sub.4 H.sub.9                                                   858                                        23   HO--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.11 --C.sub.4 H.sub.9                                          1,856                                        24   HO--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.15 --C.sub.4 H.sub.9                                          3,254                                        25   HO--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.4 --C.sub.4 H.sub.9                                           1,122                                        26   HO--[(F.sub.3 C)CH--CH.sub.2 --O].sub.20 --CH.sub.2 CF.sub.3                                              2,340                                        27   HO--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.24 --CH.sub.2 CF.sub.3                                        3,988                                        28   HO--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.4 --CH.sub.2 CF.sub.3                                           948                                        29   HO--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.8 --CH.sub.2 CF.sub.3                                         2,196                                        30   HO--[(F.sub.3 C)CH--CH.sub.2 --O].sub.21 --CH.sub.2 C.sub.3                                               2,552.7                                      31   HO--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.20 --CH.sub.2 C.sub.3             F.sub.7                     3,427                                        32   HO--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.15 --CH.sub.2 C.sub.3             F.sub.7                     3,380                                        33   HO--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.10 --CH.sub.2 C.sub.3             F.sub.7                     2,820                                        34   CH.sub.3 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.5 --CH.sub.2 CF.sub.3                                         674                                        35   CH.sub.3 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.9 --CH.sub.2              CF.sub.3                    1,572                                        36   CH.sub.3 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.13 --CH.sub.2             CF.sub.3                    2,870                                        37   CH.sub.3 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.14 --CH.sub.2             CF.sub.3                    3,782                                        38   CH.sub.3 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.8 --CH.sub.2 C.sub.3            F.sub.7                     1,110                                        39   CH.sub.3 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.7 --CH.sub.2              C.sub.3 F.sub.7             1,005                                        40   CH.sub.3 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.6 --CH.sub.2              C.sub.3 F.sub.7             1,486                                        41   CH.sub.3 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.5 --CH.sub.2              C.sub.3 F.sub.7             1,524                                        42   C.sub.2 H.sub.5 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.12 --CH.sub.2            CF.sub.3                    1,472                                        43   C.sub.2 H.sub.5 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.11                 --CH.sub.2 CF.sub.3         1,910                                        44   C.sub.2 H.sub.5 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.10                 --CH.sub.2 CF.sub.3         2,248                                        45   C.sub.2 H.sub.5 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.9                  --CH.sub.2 CF.sub.3         2,486                                         46  C.sub.2 H.sub.5 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.16 --CH.sub.2            C.sub.3 F.sub.7             2,020                                        47   C.sub.2 H.sub.5 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.15                 --CH.sub.2 C.sub.3 F.sub.7  2,658                                        48   C.sub.2 H.sub.5 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.14                 --CH.sub.2 C.sub.3 F.sub.7  3,196                                        49   C.sub.2 H.sub.5 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.13                 --CH.sub.2 C.sub.3 F.sub.7  3,634                                        50   C.sub.3 H.sub.7 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.17 --CH.sub.2            CF.sub.3                    2,063                                        51   C.sub.3 H.sub.7 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.16                 --CH.sub.2 CF.sub.3         2,734                                        52   C.sub.3 H.sub.7 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.15                 --CH.sub.2 CF.sub.3         3,322                                        53   C.sub.3 H.sub.7 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.14                 --CH.sub.2 CF.sub.3         3,810                                        54   C.sub.3 H.sub.7 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.7 --CH.sub.2             C.sub.3 F.sub.7             1,033                                        55   C.sub.3 H.sub.7 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.6                  --CH.sub.2 C.sub.3 F.sub.7  1,214                                        56   C.sub.3 H.sub.7 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.5                  --CH.sub.2 C.sub.3 F.sub.7  1,302                                        57   C.sub.3 H.sub.7 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.4                  --CH.sub.2 C.sub.3 F.sub.7  1,290                                        58   C.sub.4 H.sub.9 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.8 --CH.sub.2             CF.sub.3                    1,052                                        59   C.sub.4 H.sub.9 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.7                  --CH.sub.2 CF.sub.3         1,290                                        60   C.sub.4 H.sub.9 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.6                  --CH.sub.2 CF.sub.3         1,428                                        61   C.sub.4 H.sub.9 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub. 5                 --CH.sub.2 CF.sub.3         1,466                                        62   C.sub.4 H.sub.9 O--[(F.sub.3 C)CH--CH.sub.2 --O].sub.9 --CH.sub.2             C.sub.3 F.sub.7             1,264                                        63   C.sub.4 H.sub.9 O--[(F.sub.5 C.sub.2)CH--CH.sub.2 --O].sub.8                  --CH.sub.2 C.sub.3 F.sub.7  1,552                                        64   C.sub.4 H.sub.9 O--[(F.sub.7 C.sub.3)CH--CH.sub.2 --O].sub.7                  --CH.sub.2 C.sub.3 F.sub.7  1,740                                        65   C.sub.4 H.sub.9 O--[(F.sub.9 C.sub.4)CH--CH.sub.2 --O].sub.6                  --CH.sub.2 C.sub.3 F.sub.7  1,828                                        66   HO[(F.sub.3 C)CH--CH.sub.2 --O].sub.29 --OH                                                               3,311                                        67   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.20 OH                                                               3,274                                        68   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.8 OH                                                                1,730                                        69   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.7 OH                                                                1,868                                        70   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.30 CH.sub.3                                                       3,406                                        71   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.19 CH.sub.                                                  3,124                                        72   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.9 CH.sub.3                                                  1,954                                        73   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.8 CH.sub.3                                                  2,142                                        74   C.sub.2 H.sub.5 O[(F.sub.3 C)CHCH.sub.2 O].sub.31 C.sub.2 H.sub.5                                         3,577                                        75   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.18 C.sub.2               H.sub.5                     2,990                                        76   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.10 C.sub.2               H.sub.5                     2,194                                        77   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.9 C.sub.2                H.sub.5                     2,432                                        78   C.sub.3 H.sub.7 O[(F.sub.3 C)CHCH.sub.2 O].sub.32 C.sub.3 H.sub.7                                         3,718                                        79   C.sub.3 H.sub.7 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.17 C.sub.3               H.sub.7                     2,856                                        80   C.sub.3 H.sub.7 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.11 C.sub.3               H.sub.7                     2,434                                        81   C.sub.3 H.sub.7 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.10 C.sub.3               H.sub.7                     2,722                                        82   C.sub.4 H.sub.9 O[(F.sub.3 C)CHCH.sub.2 O].sub.33 C.sub.4 H.sub.9                                         3,859                                        83   C.sub.4 H.sub.9 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.16 C.sub.4               H.sub.9                     2,722                                        84   C.sub.4 H.sub.9 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.12 C.sub.4               H.sub.9                     2,674                                        85   C.sub.4 H.sub.9 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.11 C.sub.4               H.sub.9                     3,012                                        86   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.3 C.sub.2 H.sub.5                                                   396                                        87   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.2 C.sub.2 H.sub.5                                             384                                        88   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.2 C.sub.2 H.sub.5                                             484                                        89   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O]C.sub.2 H.sub.5                                                    322                                        90   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.4 C.sub.3 H.sub.7                                                   522                                        91   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.15 C.sub.3 H.sub.7                                          2,504                                        92   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.13 C.sub.3 H.sub.7                                          2,830                                        93   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.12 C.sub.3 H.sub.7                                          3,218                                        94   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.5 C.sub.4 H.sub.9                                                   648                                        95   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.4 C.sub.4 H.sub.9                                           2,736                                        96   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.14 C.sub.4 H.sub.9                                          3,056                                        97   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.13 C.sub.4 H.sub.9                                          3,494                                        98   C.sub.2 H.sub.5 O[(F.sub.3 C)CHCH.sub.2 O].sub.6 C.sub.3 H.sub.7                                            760                                        99   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.13 C.sub.3               H.sub.7                     2,194                                       100   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.15 C.sub.3               H.sub.7                     3,268                                       101   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.14 C.sub.3               H.sub.7                     3,756                                       102   C.sub.2 H.sub. 5 O[(F.sub.3 C)CHCH.sub.2 O].sub.7 C.sub.4 H.sub.9                                           888                                       103   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.12 C.sub.4               H.sub.9                     2,046                                       104   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.15 C.sub.4               H.sub.9                     3,275                                       105   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.14 C.sub.4               H.sub.9                     3,770                                       106   C.sub.3 H.sub.7 O[(F.sub.3 C)CHCH.sub.2 O].sub.8 C.sub.4 H.sub.9                                          1,012                                       107   C.sub.3 H.sub.7 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.11 C.sub.4               H.sub.9                     1,899                                       108   C.sub.3 H.sub.7 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.16 C.sub.4               H.sub.9                     3,508                                       109   C.sub.3 H.sub.7 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.13 C.sub.4               H.sub.9                     3,522                                       110   F.sub.3 CH.sub.2 CO[(F.sub.3 C)CHCH.sub.2 O].sub.7 CH.sub.2                   CF.sub.3                      966 966                                   ______________________________________                                    

    ______________________________________                                        111   F.sub.3 CH.sub.2 CO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.8 CH.sub.2             CF.sub.3                    1,478                                       112   F.sub.3 CH.sub.2 CO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.9 CH.sub.2             CF.sub.3                    2,090                                       113   F.sub.3 CH.sub.2 CO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.10 CH.sub.2            CF.sub.3                    2,802                                       114   F.sub.7 C.sub.3 H.sub.2 CO[(F.sub.3 C)CHCH.sub.2 O].sub.11 CH.sub.2           C.sub.3 F.sub.7             1,614                                       115   F.sub.7 C.sub.3 H.sub.2 CO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.12              CH.sub.2 C.sub.3 F.sub.7    2,326                                       116   F.sub.7 C.sub.3 H.sub.2 CO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.13              CH.sub.2 C.sub.3 F.sub.7    3,138                                       117   F.sub.7 C.sub.3 H.sub.2 CO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.13              CH.sub.2 C.sub.3 F.sub.7    3,788                                       118   F.sub.3 CH.sub.2 CO[(F.sub.3 C)CHCH.sub.2 O].sub.15 CH.sub.2                  C.sub.3 F.sub.7             1,962                                       119   F.sub.3 CH.sub.2 CO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.16 CH.sub.2            C.sub.3 F.sub. 7            2,874                                       120   F.sub.3 CH.sub.2 CO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.17 CH.sub.2            C.sub.3 F.sub.7             3,869                                       121   F.sub.3 CH.sub.2 CO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.12 CH.sub.2            C.sub.3 F.sub.7             3,426                                       122   HO[(F.sub.3 C)CHCH.sub.2 O].sub.2 [(CH.sub.2).sub.2 O]CH.sub.3                                              300                                       123   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.8 [(CH.sub.2).sub.2 O]CH.sub.3                                      1,372                                       124   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.12 [(CH.sub.2).sub.2 O]CH.sub.          3                           2,620                                       125   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.16 [(CH.sub.2).sub.2 O]CH.sub.          3                           4,268                                       126   HO[(F.sub.3 C)CHCH.sub.2 O].sub.5 [(CH.sub.2).sub.2 O]C.sub.2                 H.sub.5                       650                                       127   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.9 [(CH.sub.2).sub.2 O]C.sub.2           H.sub.5                     1,548                                       128   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.13 [(CH.sub.2).sub.2 O]C.sub.2           H.sub.5                    2,846                                       129   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.14 [(CH.sub.2).sub.2 O]C.sub.2           H.sub.5                    3,758                                       130   HO[(F.sub.3 C)CHCH.sub.2 O].sub.6 [(CH.sub.2).sub.2 O]C.sub.3                 H.sub.7                       776                                       131   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.10 [(CH.sub.2).sub.2 O]C.sub.3           H.sub.7                    1,724                                       132   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.14 [(CH.sub.2).sub.2 O]C.sub.3           H.sub.7                    3,072                                       133   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2 O]C.sub.3                  H.sub.7                       368                                       134   HO[(F.sub.3 C)CHCH.sub.2 O].sub.7 [(CH.sub.2).sub.2 O]C.sub.4                 H.sub.9                       902                                       135   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.11 [(CH.sub.2).sub.2 O]C.sub.4           H.sub.9                    1,900                                       136   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.15 [(CH.sub.2).sub.2 O]C.sub.4           H.sub.9                    3,298                                       137   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.2 [(CH.sub.2).sub.2 O]C.sub.4           H.sub.9                       649                                       138   HO[(F.sub.3 C)CHCH.sub.2 O].sub. 20 [(CH.sub.2).sub.2 O]CH.sub.2              CF.sub.3                    2,404                                       139   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.23 [(CH.sub.2).sub.2 O]CH.sub.          2 CF.sub.3                  3,870                                       140   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.16 [(CH.sub.2).sub.2 O]CH.sub.          2 CF.sub.3                  3,536                                       141   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.3 [(CH.sub.2).sub.2 O]CH.sub.2           CF.sub.3                     930                                       142   HO[(F.sub.3 C)CHCH.sub.2 O].sub.21 [(CH.sub.2).sub.2 O]CH.sub.2               C.sub.3 F.sub.7             2,617                                       143   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.22 [(CH.sub.2).sub.2 O]CH.sub.          2 C.sub.3 F.sub.7           3,808                                       144   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.15 [(CH.sub.2).sub.2 O]CH.sub.          2 C.sub.3 F.sub.7           3,424                                       145   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.4 [(CH.sub.2).sub.2 O]CH.sub.2           C.sub.3 F.sub.7            1,292                                       146   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.22 [(CH.sub.2).sub.2                  O]CH.sub.2 CF.sub.3         2,644                                       147   CH.sub.3 O[ (F.sub.5 C.sub.2)CHCH.sub.2 O].sub.21 [(CH.sub.2).sub.2           O]CH.sub.2 CF.sub.3         3,560                                       148   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.14 [(CH.sub.2).sub.2            O]CH.sub.2 CF.sub.3         3,126                                       149   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.5 [(CH.sub.2).sub.2             O]CH.sub.2 CF.sub.3         1,468                                       150   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.21 [(CH.sub.2).sub.2                  O]CH.sub.2 CF.sub.3         2,631                                       151   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O][(CH.sub.2).sub.2 O]CH.sub.          2 CF.sub.3                    420                                       152   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O][(CH.sub.2).sub.2 O]CH.sub.          2 CF.sub.3                    470                                       153   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2 O]CH.sub.          2 CF.sub.3                    520                                       154   C.sub.2 H.sub.5 O[(F.sub.3 C)CHCH.sub.2 O].sub.23 [(CH.sub.2).sub.2           O]CH.sub.2 CF.sub.3         2,748                                       155   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2)CHCH.sub.2 O][ (CH.sub.2).sub.2            O]CH.sub.2 CF.sub.3           334                                       156   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.12 [(CH.sub.2).          sub.2 O]CH.sub.2 CF.sub.3   2,716                                       157   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.7 [(CH.sub.2).s          ub.2 O]CH.sub.2 CF.sub.3    2,006                                       158   C.sub.2 H.sub.5 O[(F.sub.3 C)CHCH.sub.2 O].sub.24 [(CH.sub.2).sub.2           O]CH.sub.2 CF.sub.3         2,960                                       159   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    435                                       160   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    469                                       161   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    563                                       162   C.sub.3 H.sub.7 O[(F.sub.3 C)CHCH.sub.2 O].sub.25 [(CH.sub.2).sub.2           O]CH.sub.2 CF.sub.3         3,011                                       163   C.sub.3 H.sub. 7 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.19 [(CH.sub.2)          .sub.2 O]CH.sub.2 CF.sub.3  3,264                                       164   C.sub.3 H.sub.7 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.2 [(CH.sub.2).s          ub.2 O]CH.sub.2 CF.sub.3      610                                       165   C.sub.3 H.sub.7 O[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 CF.sub.3           448                                       166   C.sub.3 H.sub.7 O[(F.sub.3 C)CHCH.sub.2 O].sub.26 [(CH.sub.2).sub.2           O]CH.sub.2 C.sub.3 F.sub.7  3,198                                       167   C.sub.3 H.sub.7 O[(F.sub.5 C.sub.2)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    449                                       168   C.sub.3 H.sub.7 O[(F.sub.7 C.sub.3)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    498                                       169   C.sub.3 H.sub.7 O[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    548                                       170   C.sub.4 H.sub.9 O[(F.sub.3 C)CHCH.sub.2 O].sub.27 [                           (CH.sub.2).sub.2 O]CH.sub.2 CF.sub.3                                                                      3,251                                       171   C.sub.4 H.sub.9 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.6 [(CH.sub.2).s          ub.2 O]CH.sub.2 CF.sub.3    1,172                                       172   C.sub.4 H.sub.9 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.5 [(CH.sub.2).s          ub.2 O]CH.sub.2 CF.sub.3    1,260                                       173   C.sub.4 H.sub.9 O[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 CF.sub.3           462                                       174   C.sub.4 H.sub.9 O[(F.sub.3 C)CHCH.sub.2 O].sub.28 [(CH.sub.2).sub.2           O]CH.sub.2 C.sub.3 F.sub.7  3,464                                       175   C.sub.4 H.sub.9 O[(F.sub.5 C.sub.2)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    486                                       176   C.sub.4 H.sub.9 O[(F.sub.7 C.sub.3)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    512                                       177   C.sub.4 H.sub.9 O[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2             O]CH.sub.2 C.sub.3 F.sub.7    562                                       178   HO[ (F.sub.3 C)CHCH.sub.2 O].sub.29 [(CH.sub.2).sub.2 O]OH                                                3,326                                       179   HO[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.3 [(CH.sub.2).sub.2 O]OH                                              564                                       180   HO[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.3 [(CH.sub.2).sub.2 O]OH                                              502                                       181   HO[(F.sub.9 C.sub.4)CHCH.sub.2 O][(CH.sub.2).sub.2 O]OH                                                     340                                       182   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.4 [(CH.sub.2).sub.2                   O]CH.sub.3                    538                                       183   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.5 [(CH.sub.2).sub.2             O]CH.sub.3                    900                                       184   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.6 [(CH.sub.2).sub.2             O]CH.sub.3                  1,362                                       185   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.7 [(CH.sub.2).sub.2             O]CH.sub.3                  1,924                                       186   C.sub.2 H.sub.5 O[(F.sub.3 C)CHCH.sub.2 O].sub.8 [(CH.sub.2).sub.2            O]C.sub.2 H.sub.5           1,014                                       187   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2 )CHCH.sub.2 O].sub.9 [(CH.sub.2).          sub.2 O]C.sub.2 H.sub.5     1,576                                       188   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.10 [(CH.sub.2).          sub.2 O]C.sub.2 H.sub.5     2,238                                       189   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.11 [(CH.sub.2).          sub.2 O]C.sub.2 H.sub.5     3,000                                       190   C.sub.3 H.sub.7 O[(F.sub.3 C)CHCH.sub.2 O].sub.12 [(CH.sub.2).sub.2           O]C.sub.3 H.sub.7           1,490                                       191   C.sub.3 H.sub.7 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.13 [(CH.sub.2).          sub.2 O]C.sub.3 H.sub.7     2,252                                       192   C.sub.3 H.sub.7 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.14 [(CH.sub.2).          sub.2 O]C.sub.3 H.sub.7     3,114                                       193   C.sub.3 H.sub.7 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.14 [(CH.sub.2).          sub.2 O]C.sub.3 H.sub.7     3,814                                       194   C.sub.4 H.sub.9 O[(F.sub.3 C)CHCH.sub.2 O].sub.16 [(CH.sub.2).sub.2           O]C.sub.4 H.sub.9           1,966                                       195   C.sub.4 H.sub.9 O[ (F.sub.5 C.sub.2)CHCH.sub.2 O].sub.17 [(CH.sub.2)          .sub.2 O]C.sub.4 H.sub.9    2,928                                       196   C.sub.4 H.sub.9 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.18 [(CH.sub.2).          sub.2 O]C.sub.4 H.sub.9     3,990                                       197   C.sub.4 H.sub.9 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.12 [(CH.sub.2).          sub.2 O]C.sub.4 H.sub.9     3,318                                       198   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.20 [(CH.sub.2).sub.2                  O]C.sub.2 H.sub.5           2,344                                       199   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.21 [(CH.sub.2).sub.2            O]C.sub.2 H.sub.5           3,506                                       200   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.15 [(CH.sub.2).sub.2            O]C.sub.2 H.sub.5           3,284                                       201   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.10 [(CH.sub.2).sub.2            O]C.sub.2 H.sub.5           2,724                                       202   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.24 [(CH.sub.2).sub.2                  O]C.sub.3 H.sub.7           2,806                                       203   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub. 23 [(CH.sub.2).sub.2           O]C.sub.3 H.sub.7           3,844                                       204   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.14 [(CH.sub.2).sub.2            O]C.sub.3 H.sub.7           3,086                                       205   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.9 [(CH.sub.2).sub.2             O]C.sub.3 H.sub.7           2,476                                       206   CH.sub.3 O[(F.sub.3 C)CHCH.sub.2 O].sub.28 [(CH.sub.2).sub.2                  O]C.sub.4 H.sub.9           3,268                                       207   CH.sub.3 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.20 [(CH.sub.2).sub.2            O]C.sub.4 H.sub.9           3,372                                       208   CH.sub.3 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.13 [(CH.sub.2).sub.2            O]C.sub.4 H.sub.9           2,888                                       209   CH.sub.3 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.8 [(CH.sub.2).sub.2             O]C.sub.4 H.sub.9           2,228                                       210   C.sub.2 H.sub.5 O[(F.sub.3 C)CHCH.sub.2 O].sub.32 [(CH.sub.2).sub.2           O]C.sub.3 H.sub.7           3,716                                       211   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.19 [(CH.sub.2).          sub.2 O] C.sub.3 H.sub.7    3,210                                       212   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.12 [(CH.sub.2).          sub.2 O]C.sub.3 H.sub.7     1,965                                       213   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.7 [(CH.sub.2).s          ub.2 O]C.sub.3 H.sub.7      1,965                                       214   C.sub.2 H.sub.5 O[(F.sub.3 C)CHCH.sub.2 O].sub.30 [(CH.sub.2).sub.2           O]C.sub.4 H.sub.9           3,506                                       215   C.sub.2 H.sub.5 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.18 [(CH.sub.2).          sub.2 O]C.sub.4 H.sub.9     3,055                                       216   C.sub.2 H.sub.5 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.11 [(CH.sub.2).          sub.2 O]C.sub.4 H.sub.9     2,478                                       217   C.sub.2 H.sub.5 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.6 [(CH.sub.2).s          ub.2 O]C.sub.4 H.sub.9      1,718                                       218   C.sub.3 H.sub.7 O[(F.sub.3 C)CHCH.sub.2 O].sub.29 [(CH.sub.2).sub.2           O]C.sub.4 H.sub.9           3,408                                       219   C.sub.3 H.sub.7 O[(F.sub.5 C.sub.2)CHCH.sub.2 O].sub.17 [(CH.sub.             2).sub.2 O]C.sub.4 H.sub.9  2,914                                       220   C.sub.3 H.sub.7 O[(F.sub.7 C.sub.3)CHCH.sub.2 O].sub.10 [(CH.sub.2).          sub.2 O]C.sub.4 H.sub.9     1,470                                       221   C.sub.3 H.sub.7 O[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.5 [(CH.sub.2).s          ub.2 O]C.sub.4 H.sub.9      1,470                                       222   F.sub.3 CH.sub.2 CO[(F.sub.3 C)CHCH.sub.2 O].sub.7 [(CH.sub.2).sub.2           O]CH.sub.2 CF.sub.3        1,010                                       223   F.sub.3 CH.sub.2 CO[(F.sub.5 C.sub.2)CHCH.sub.2 O][(CH.sub.2).sub.2           O]CH.sub.2 CF.sub.3           388                                       224   F.sub.3 CH.sub.2 CO[(F.sub.7 C.sub.3)CHCH.sub.2 O][(CH.sub.2).sub.2           O]CH.sub.2 CF.sub.3           413                                       225   F.sub.3 CH.sub.2 CO[(F.sub.9 C.sub.4)CHCH.sub.2 O].sub.7 [(CH.sub.2)          .sub.2 O]CH.sub.2 CF.sub.3    488                                       ______________________________________                                    

Having described the invention in detail and by reference to preferredembodiments thereof, it will be apparent that modifications andvariations are possible without departing from the scope of theinvention defined in the appended claims.

What is claimed is:
 1. A composition for use in compressionrefrigeration and air-conditioning comprising:(a) at least onerefrigerant selected from the group consisting of hydrofluorocarbon,hydrochlorofluorocarbon, fluorocarbon, and chlorofluorocarbon; and (b) asufficient amount to provide lubrication of at least one polyoxyalkyleneglycol wherein said polyoxyalkylene glycol has a molecular weightbetween about 300 and about 4,000 has a viscosity of about 5 to about300 centistokes at 37° C., and has at least one pendant non-terminalperfluorinated alkyl group.
 2. The composition of claim 1 wherein saidpolyoxyalkylene glycol is prepared by reacting a partially fluorinatedepoxy alkane.
 3. The composition of claim 1 wherein in addition to saidat least one pendant non-terminal perfluorinated alkyl group on thehydrocarbon polymer backbone, said polyoxyalkylene glycol has pendantnon-terminal alkyl groups on said hydrocarbon polymer backbone.
 4. Thecomposition of claim 1 wherein said refrigerant is a hydrofluorocarbon.5. The composition of claim 4 wherein said hydrofluorocarbon istetrafluoroethane.
 6. The composition of claim 5 wherein saidtetrafluoroethane is 1,1,1,2-tetrafluoroethane.
 7. The composition ofclaim 3 wherein of the total number of pendant, non-terminalperfluorinated alkyl groups and pendant, non-terminal alkyl groups insaid polyoxyalkylene glycol, at least 40% are pendant, non-terminalperfluorinated alkyl groups.
 8. The composition of claim 1 wherein thepolyoxyalkylene glycol is miscible in combination with the refrigerantin the range between -40° C. and at least +20° C.
 9. The composition ofclaim 1 wherein said polyoxyalkylene glycol is of the formula

    R'O--[(R.sub.f)CH--CH.sub.2 --O].sub.m [RCHCH.sub.2 O].sub.n R'

wherein R' is selected from the group consisting of hydrogen, alkyl, orfluoroalkyl; m is 2 to 40; n is 0 to 60; R is selected from the groupconsisting of hydrogen and alkyl group; and R_(f) is a perfluoroalkylgroup.
 10. The composition of claim 9 wherein at least one R' ishydrogen.
 11. The composition of claim 9 wherein at least one R' is analkyl group having 1 to 12 carbon atoms.
 12. The composition of claim 9wherein at least one R' is a fluoroalkyl group of the formula

    --(CH.sub.2).sub.x (CF.sub.2).sub.y CF.sub.3

wherein x is 1 to 4 and y is 0 to
 15. 13. The composition of claim 8wherein R_(f) is a perfluoroalkyl group selected from the groupconsisting of perfluoromethyl, perfluoroethyl, perfluoropropyl,perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, andperfluorooctyl.
 14. The composition of claim 10 wherein saidpolyoxyalkylene glycol is of the formula

    HO--[(R.sub.f)CH--CH.sub.2 --O].sub.m [RCHCH.sub.2 O].sub.n H

wherein m is 4 to 40 and n=40-m.
 15. The composition of claim 11 whereinsaid polyoxyalkylene glycol is of the formula

    CH.sub.3 O--[(R.sub.f)CH--CH.sub.2 --O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.3

wherein m is 4 to 40 and n=40-m.
 16. The composition of claim 12 whereinsaid polyoxyalkylene glycol is of the formula

    CF.sub.3 CH.sub.2)--[(R.sub.f)CH--CH.sub.2 --O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.2 CF.sub.3

wherein m is 4 to 40 and n=40-m.
 17. The composition of claim 12 whereinsaid polyoxyalkylene glycol is of the formula

    F.sub.7 C.sub.3 CH.sub.2 O[(R.sub.f)CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.2 C.sub.3 F.sub.7

wherein m is 4 to 40 and n=40-m.
 18. The composition of claim 10 whereinsaid polyoxyalkylene glycol is of the formula

    HO--[(R.sub.f)CH--CH.sub.2 --O].sub.m [RCHCH.sub.2 O].sub.n H

wherein the ratio of m to n is at least 2:3.
 19. The composition ofclaim 11 wherein said polyoxyalkylene glycol is of the formula

    CH.sub.3 O--[(R.sub.f)CH--CH.sub.2 --O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.3

wherein the ratio of m to n is at least 2:3.
 20. The composition ofclaim 12 wherein said polyoxyalkylene glycol is of the formula

    CF.sub.3 CH.sub.2 O[(R.sub.f)CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.2 CF.sub.3

wherein the ratio of m to n is at least 2:3.
 21. The composition ofclaim 12 wherein said polyoxyalkylene glycol is of the formula

    F.sub.7 C.sub.3 CH.sub.2 O[(R.sub.f)CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n CH.sub.2 C.sub.3 F.sub.7

wherein the ratio of m to n is at least 2:3.
 22. A method for improvinglubrication in compression refrigeration and air-conditioning equipmentusing a refrigerant selected from the group consisting ofhydrofluorocarbon, hydrochlorofluorocarbon, fluorocarbon, andchlorofluorocarbon comprising the step of:employing as a lubricant atleast one polyoxyalkylene glycol wherein said polyoxyalkylene glycol hasa molecular weight between about 300 and 4,000, has a viscosity of about5 to about 300 centistokes at 37° C., and has at least one pendantnon-terminal perfluorinated alkyl group.
 23. The method of claim 22wherein said polyoxyalkylene glycol is of the formula

    R'O[(R.sub.f)CHCH.sub.2 O].sub.m [RCHCH.sub.2 O].sub.n R'

wherein R' is selected from the group consisting of hydrogen, alkyl, orfluoroalkyl; m is 2 to 40; n is 0 to 60; R_(f) is a perfluoroalkylgroup; and R is selected from the group consisting of hydrogen and alkylgroup.